Catalyst compositions containing modified beta molecular sieves and applications

Abstract

The application provides a catalyst composition and application thereof, and the catalyst composition comprises: 5-20 wt% of modified Beta molecular sieve, wherein the particle size of the modified Beta molecular sieve is 100-300 nm, the meso-macropore volume is 0.15-0.40 cm 3 / g, the volume of the meso-macropore accounts for 40%-60% of the total pore volume, the crystallinity is 80%-160%, the SiO2 / Al2O3 is 20-200; 20-40 wt% of USY type molecular sieve; 40-50 wt% of catalyst carrier; 10-20 wt% of binder; and 0-20 wt% of ZSM-5 molecular sieve. The catalyst composition of the application can improve the total yield of ethylene, propylene and butene, increase the yield of gasoline, increase the yield of diesel oil and reduce the yield of coke when used for catalytic cracking of heavy oil.

Description

Technical Field

[0001] This invention relates to a method for modifying raw material Beta molecular sieves and preparing catalysts thereof, and its application. In particular, it relates to a method for modifying raw material Beta molecular sieves with rod-shaped, small crystals and preparing catalysts thereof, and its application, belonging to the field of molecular sieve materials and their preparation technology. Background Technology

[0002] Zeolite molecular sieves, characterized by their micropores, play a crucial role in adsorption separation, ion exchange, and heterogeneous catalysis. The pore sizes of zeolite molecular sieves are generally less than 1 nm and vary considerably, allowing for the sieving of molecules of different sizes. In particular, many microporous and mesoporous zeolite molecular sieves (eight-membered and ten-membered rings) exhibit unique shape-selective properties, holding exceptionally important positions in heterogeneous catalysis. However, the diffusion restriction of large molecules within the micropores severely limits the application of zeolite molecular sieves in catalytic reactions.

[0003] my country is a major consumer of fuel oil, and effectively improving the catalyst's ability to process large heavy oil molecules is key to increasing the yield of fuel oil from the catalytic cracking of heavy oil macromolecules. Zeolite molecular sieves, as the main active component in heavy oil conversion catalysts, play a crucial role in the cracking of large heavy oil molecules through their diffusion properties. Improving their diffusion capacity can better address the conversion problem of heavy feedstock oil.

[0004] The preparation of zeolite molecular sieves with mesoporous-microporous composite channels has become a research hotspot. Among the methods for preparing hierarchical porous zeolite molecular sieves, post-treatment methods involving dealumination, desilication, or structural rearrangement are commonly used. The raw material, Beta molecular sieve, has a high framework silica-alumina ratio, low hydrogen transfer reactivity, and an average pore size between Y-type and ZSM-5 molecular sieves, exhibiting excellent C4 olefin selectivity. Therefore, developing a modified Beta molecular sieve and using existing processes to prepare it into a catalyst will significantly improve the performance of refining catalysts, drive technological advancements in refining catalysts, and bring substantial social and economic benefits. Summary of the Invention

[0005] In view of this, in order to solve one of the above problems, a raw material molecular sieve modified catalyst, catalyst composition, method and application thereof are provided, which have one of the following effects: increased total yield of ethylene, propylene and butene, or increased gasoline yield, or increased diesel yield, or decreased coke yield. In addition, this application also provides a method for preparing modified Beta molecular sieves, various applications of modified Beta molecular sieves such as single catalytic use, combined use of modified Beta molecular sieves, and relates to the significant effect of Beta molecular sieve catalysts in catalytic cracking applications.

[0006] This invention includes the following:

[0007] Embodiment 1, a catalyst composition comprising:

[0008] 5-20 wt% modified Beta molecular sieve, wherein the modified Beta molecular sieve is free of template agent, the particle size of the modified Beta molecular sieve is 100-300 nm, and the meso-macropore volume of the modified Beta molecular sieve is 0.15-0.40 cm³. 3 / g, the volume of meso-macropores accounts for 40%-60% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80%-160%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 20-200.

[0009] 20-40 wt% USY type molecular sieve;

[0010] 40-50 wt% catalyst support;

[0011] 10-20 wt% binder; and

[0012] 0-20wt% ZSM-5 molecular sieve,

[0013] The total mass of the catalyst composition is 100 wt%.

[0014] Implementation Method 2. The catalyst composition according to Implementation Method 1 is prepared by the following steps:

[0015] Step 1: Mix all components evenly, shape, and age in water vapor to obtain the aged composition;

[0016] Step 2: The aged composition is sieved and calcined to obtain the catalyst composition, wherein the mesopore volume value of the catalyst composition is greater than or equal to 25% of the mesopore volume value of the modified Beta molecular sieve, preferably 33%, and the ratio of the volume of meso-macropores in the catalyst composition to the total pore volume is greater than or equal to 110% of the ratio of the volume of meso-macropores in the modified Beta molecular sieve to the total pore volume, preferably 120%.

[0017] Implementation Method 3. According to the catalyst composition of Implementation Method 2, the aging in step one is carried out in water vapor with a concentration of 40% or higher at 300 to 900°C for 2 to 10 hours.

[0018] Implementation Method 4. According to the catalyst composition described in Implementation Method 2, the sieving in step two refers to sieving the aged composition into 50 mesh to 500 mesh, and the calcination refers to calcining at a temperature of 200 to 500°C for 1 to 5 hours.

[0019] Embodiment 5. The modified Beta molecular sieve according to the catalyst composition of Embodiment 2 is prepared as follows:

[0020] The template agent is completely removed from the raw material Beta molecular sieve containing the template agent to obtain the template agent-free raw material Beta molecular sieve;

[0021] The modified Beta molecular sieve is obtained by cycling the template-removed Beta molecular sieve through at least one or at least two of the following steps: ammonium ion exchange or hydrogen ion exchange, followed by high-temperature calcination or hydrothermal treatment.

[0022] Implementation Method 6. According to the catalyst composition of Implementation Method 2, the preparation of the raw material Beta molecular sieve containing the template agent includes the following steps: Step 1, aluminum source, alkali source and template agent are added sequentially to a solvent, stirred into a solution, and then aged to obtain intermediate product A;

[0023] Step 2: Take another solvent, add silicon source, seed crystal and additive, stir until completely dissolved, add intermediate product A from step 1, and then add aluminum source to obtain alkaline gel B;

[0024] Step 3: Crystallize the alkaline gel B obtained in Step 2 to obtain the raw material Beta molecular sieve;

[0025] The amount of template agent used is 2% to 10% of the aluminum source in molar terms. The raw material Beta molecular sieve is rod-shaped or has small crystals. The particle size of the raw material Beta molecular sieve is 100-300 nanometers. The utilization rate of the aluminum source is greater than or equal to 90%. The utilization rate of the silicon source is greater than or equal to 83%. The crystallinity of the raw material Beta molecular sieve is greater than or equal to 93%.

[0026] Embodiment 7. According to the catalyst composition of Embodiment 1, the silica-alumina ratio of the USY molecular sieve is 10 to 100, for example 20 to 80, 30 to 40.

[0027] Embodiment 8. The catalyst composition according to Embodiment 1, wherein the content of the modified Beta molecular sieve is 10-15 wt%.

[0028] Embodiment 9. The catalyst composition according to Embodiment 1, wherein the binder is aluminum sol and the catalyst support is kaolin.

[0029] Embodiment 10. This application also provides a method for carrying out catalytic cracking or hydrocracking reactions, wherein the catalyst composition described in any one of Embodiments 1 to 9 is used as the catalyst.

[0030] Implementation Method 11. The method according to Implementation Method 10 is used to carry out catalytic cracking or hydrocracking of heavy oil.

[0031] Implementation Method 12. This application also provides a method for preparing modified Beta molecular sieves, comprising the following steps:

[0032] The template agent is completely removed from the raw material Beta molecular sieve containing the template agent to obtain the template agent-free raw material Beta molecular sieve;

[0033] The modified Beta molecular sieve is obtained by cycling the template-removed Beta molecular sieve through at least one or at least two of the following steps: ammonium ion exchange or hydrogen ion exchange, followed by high-temperature calcination or hydrothermal treatment.

[0034] Implementation Method 13. This application also provides a method for preparing a raw material Beta molecular sieve as follows: including the following steps:

[0035] Step 1: Add aluminum source, alkali source, and template agent to the solvent in sequence, stir to form a solution, and continue aging to obtain intermediate product A;

[0036] Step 2: Take another solvent, add silicon source, seed crystal and additive, stir until completely dissolved, add intermediate product A from step 1, and then add aluminum source to obtain alkaline gel B;

[0037] Step 3: Crystallize the alkaline gel B obtained in Step 2 to obtain the raw material Beta molecular sieve;

[0038] The template agent is used in an amount of 2% to 10% (molar) of the aluminum source. The Beta molecular sieve is rod-shaped or has small crystals. The particle size of the raw material Beta molecular sieve is 100-300 nanometers. The utilization rate of the aluminum source is greater than or equal to 90%, the utilization rate of the silicon source is greater than or equal to 83%, and the crystallinity of the raw material Beta molecular sieve is greater than or equal to 93%. Furthermore, the technical solution of this invention brings many other advantages, which will be described in detail in specific embodiments.

[0039] This application has at least one of the following effects.

[0040] The catalyst composition of this application has excellent pore structure data, and the catalyst cracking effect of the composition is significant, specifically manifested in one of the following: increased total yield of ethylene, propylene and butene, or increased gasoline yield, or increased diesel yield, or decreased coke yield. The catalyst support of this application includes kaolin, and the binder includes alumina sol.

[0041] Furthermore, when the modified Beta molecular sieve is used as an additive for catalytic cracking catalysts and catalytic hydrogenation catalysts, the catalytic activity of the catalyst can be significantly improved. Attached Figure Description

[0042] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings of the embodiments will be briefly described below. Obviously, the drawings described below only relate to some embodiments of the present invention and are not intended to limit the present invention.

[0043] Figure 1 This is a SEM image of the Beta molecular sieve containing the template agent synthesized in Example 4. Detailed Implementation

[0044] Exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, these exemplary embodiments can be implemented in many forms and should not be construed as limited to the embodiments set forth herein; rather, they are provided so that the invention will be thorough and complete, and the concept of the exemplary embodiments will be fully conveyed to those skilled in the art. The same reference numerals in the drawings denote the same or similar parts, and therefore repeated descriptions of them will be omitted.

[0045] Furthermore, the described features, structures, or characteristics can be combined in any suitable manner in one or more embodiments. Numerous specific details are provided in the following description to give a full understanding of embodiments of the invention. However, those skilled in the art will recognize that the technical solutions of the invention can be practiced without one or more of the specific details, or other methods, components, apparatuses, steps, etc., can be employed. In other instances, well-known methods, apparatuses, implementations, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

[0046] In the following embodiments, the textural properties of the samples were obtained using low-temperature nitrogen physical adsorption-desorption experiments. The instrument used was a Micromeritics TriSTAR 3020 physical adsorption instrument. Test steps and methods: A certain mass of sample was taken based on the estimated surface area and dried at 120°C. Then, it was placed in a sample tube and treated for dehydration and degassing at 350°C under a vacuum (approximately 1.33 Pa) for 8 hours. The specific surface area of ​​the sample was calculated using the BET formula. The pore size distribution curve was obtained from the isothermal adsorption branch using the BJH method. The micropore specific surface area and pore volume were obtained using the t-plot method. The total pore volume of the sample was obtained at a relative pressure of 0.9944.

[0047] In the following embodiments, the reactivity of the catalyst was evaluated using heavy oil catalytic cracking reaction, with vacuum gas oil (VGO) as feedstock, and the equipment used was the Advanced Catalyst Evaluation (ACE) R+ catalyst evaluation system designed and manufactured by KTI Technologies, Inc., USA. Evaluation conditions: catalyst-to-oil ratio of 7, weight hourly space velocity (WHSV) of 2.2 × 10⁻⁶. -3 s -1The reaction temperature was 530℃. The resulting gaseous products were analyzed by online refinery gas analysis chromatography, and the liquid products were analyzed by simulated distillation chromatography to determine the gasoline and diesel fraction content. Catalyst carbon deposits were regenerated online, and the carbon deposit content was obtained using a carbon dioxide analyzer.

[0048] One aspect of the present invention provides a catalyst composition comprising:

[0049] 5-20 wt% modified Beta molecular sieve, wherein the modified Beta molecular sieve is free of template agent, the particle size of the modified Beta molecular sieve is 100-300 nm, and the meso-macropore volume of the modified Beta molecular sieve is 0.15-0.40 cm³. 3 / g, the volume of meso-macropores accounts for 40%-60% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80%-160%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 20-200.

[0050] 20-40 wt% USY type molecular sieve;

[0051] 40-50 wt% catalyst support;

[0052] 10-20 wt% binder; and

[0053] 0-20wt% ZSM-5 molecular sieve,

[0054] The total mass of the catalyst composition is 100 wt%. The catalyst composition of this application has excellent pore structure data, and the catalyst cracking effect of the composition is significant, specifically manifested in one of the following: increased total yield of ethylene, propylene, and butene, or increased gasoline yield, or increased diesel yield, or decreased coke yield.

[0055] In some embodiments, the catalyst composition is prepared by the following steps:

[0056] Step 1: Mix all components evenly, shape, and age in water vapor to obtain the aged composition;

[0057] Step 2: The aged composition is sieved and calcined to obtain the catalyst composition, wherein the mesopore volume value of the catalyst composition is greater than or equal to 25% of the mesopore volume value of the modified Beta molecular sieve, preferably 33%, and the ratio of the volume of meso-macropores in the catalyst composition to the total pore volume is greater than or equal to 110% of the ratio of the volume of meso-macropores in the modified Beta molecular sieve to the total pore volume, preferably 120%.

[0058] In some implementations, the aging in step one is carried out in water vapor with a concentration of more than 40% at 300 to 900°C for 2 to 10 hours.

[0059] In some embodiments, sieving in step two refers to sieving the aged composition into 50 to 500 mesh, and calcination refers to calcining at a temperature of 200 to 500°C for 1 to 5 hours.

[0060] In some embodiments, the modified Beta molecular sieve is prepared as follows:

[0061] The template agent is completely removed from the raw material Beta molecular sieve containing the template agent to obtain template agent-free Beta molecular sieve;

[0062] The modified Beta molecular sieve is obtained by cycling the template-removed Beta molecular sieve through at least one or at least two of the following steps: ammonium ion exchange or hydrogen ion exchange, followed by high-temperature calcination or hydrothermal treatment; the modified Beta molecular sieve is used as an additive for catalytic cracking catalysts and catalytic hydrogenation catalysts. When the modified Beta molecular sieve provided by the present invention is used as an additive for catalysts, the catalytic activity of the catalyst can be significantly improved.

[0063] A method for modifying raw material Beta molecular sieves further includes the following steps:

[0064] Step 1: Completely remove the template agent from the rod-shaped, small-crystal Beta molecular sieve raw material;

[0065] Step 2: The raw material Beta molecular sieve after template agent removal is subjected to ion exchange or hydrogen ion exchange for a certain period of time, followed by filtration, washing, and drying.

[0066] Step 3: The ammonium or hydrogen form Beta molecular sieve obtained in Step 2 is subjected to high-temperature calcination or hydrothermal treatment to obtain modified Beta molecular sieve.

[0067] Furthermore, the method also includes the following steps:

[0068] Step 1: Completely remove the template agent from the rod-shaped, small-crystal Beta molecular sieve raw material;

[0069] Step 2: Mix the template agent-removed Beta molecular sieve, ammonium salt or acid, and water evenly, stir to carry out ion exchange, process for a certain period of time, filter, wash, and dry to obtain the ammonium or hydrogen form Beta molecular sieve.

[0070] Step 3: High-temperature calcination or hydrothermal treatment of the ammonium or hydrogen form Beta molecular sieve raw material;

[0071] Repeat the above ion exchange and high-temperature calcination / hydrothermal treatment once or multiple times to obtain the modified Beta molecular sieve.

[0072] Furthermore, in step one, the rod-shaped, small-crystal Beta molecular sieve raw material has a crystallinity of 80%-160%, a SiO2 / Al2O3 ratio of 20-200, and a particle size of 100-300 nm.

[0073] Furthermore, in step one, the temperature at which the template agent is completely removed from the rod-shaped, small-crystal Beta molecular sieve is 400℃-650℃ and the time is 1.5h-6h. Preferably, the calcination temperature is 400℃-600℃ and the time is 2h-4h.

[0074] Furthermore, in step two, the stirring temperature is 20℃-95℃, the stirring time is 0.2h-4h, and the pH is adjusted to 2-7 during the stirring process.

[0075] Furthermore, the high-temperature hydrothermal treatment is carried out in a water vapor atmosphere of 10%-100%. Preferably, the temperature of the high-temperature hydrothermal treatment is 400℃-800℃ and the time of the high-temperature hydrothermal treatment is 0.5h-6h; the temperature of the high-temperature calcination treatment is 500℃-800℃ and the time of the high-temperature hydrothermal treatment is 0.5h-6h.

[0076] Furthermore, in step one of the Beta molecular sieve modification method, the rod-shaped, small-crystal Beta molecular sieve, in the form of oxides, has the following characteristics: the molar ratio of SiO2 to Al2O3 in the synthetic gel is 6-80:1; the molar ratio of Na2O to Al2O3 in the synthetic gel is 0.2-2.0:1; the molar ratio of template agent to Al2O3 in the synthetic gel is 0.02-0.1:1; the molar ratio of additive to Al2O3 in the synthetic gel is 0.01-0.06:1; and the seed crystals account for 2%-15% of the mass of the synthetic gel.

[0077] Furthermore, the modified Beta molecular sieve has a mesoporous-macropore volume; more preferably, the mesoporous-macropore volume of the modified Beta molecular sieve containing mesopores is 0.15-0.40 cm³. 3 / g, the volume of meso-macropores accounts for 40%-60% of the total pore volume.

[0078] Furthermore, the modified Beta molecular sieve can be used as an additive in catalytic hydrogenation catalysts, either alone or in combination with Y-type molecular sieves or ZSM-5 type molecular sieves.

[0079] Preferably, the modified Beta molecular sieve is used as an additive in catalytic hydrogenation catalysts, with a content of 5%-35%, and more preferably, a content of 10%-20%.

[0080] In some embodiments, the preparation of the template agent-containing Beta molecular sieve includes the following steps:

[0081] Step 1: Add aluminum source, alkali source, and template agent to the solvent in sequence, stir to form a solution, and continue aging to obtain intermediate product A. In Step 1, the aluminum source, alkali source, template agent, and solvent (such as deionized water) are in the following molar ratio: Al2O3:0.1~1.2 Na2O:0.04~0.2 Template agent:40~100 Solvent (such as deionized water).

[0082] Step 2: Take another solvent, add silicon source, seed crystal and additive, stir until completely dissolved, add intermediate product A from step 1, and then add aluminum source to obtain alkaline gel B;

[0083] Step 3: Crystallize the alkaline gel B from step 2 to obtain the raw material Beta molecular sieve;

[0084] The amount of template agent used is 2% to 10% of the aluminum source in molar terms. The particle size of the raw material Beta molecular sieve is 100-300 nanometers. The utilization rate of the aluminum source is greater than or equal to 90%. The utilization rate of the silicon source is greater than or equal to 83%. The crystallinity of the raw material Beta molecular sieve is 90%-160%.

[0085] Furthermore, the crystallinity of the raw material Beta molecular sieve is 93%-160%, the solvent is deionized water, and the crystallization is dynamic crystallization or segmented crystallization;

[0086] In the entire reaction, the silicon source, aluminum source, alkali source, template agent, additive, and deionized water are mixed in a molar ratio of 6–80 (SiO2:Al2O3:0.2–2.0, Na2O:0.02–0.1, template agent:0.01–0.06, additive:80–200) to obtain the alkaline gel, wherein the content of seed crystals in the gel is 1 wt% to 18 wt%.

[0087] Furthermore, the silicon source is one or a mixture of several of water glass, sodium silicate, solid silica gel, and precipitated silica, and the aluminum source is one or a mixture of several of boehmite, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum oxide, and aluminum chloride.

[0088] Furthermore, the alkali source is one or a mixture of two of sodium hydroxide and potassium hydroxide.

[0089] Furthermore, the template agent is one or a mixture of more than one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

[0090] Furthermore, the additive is an alcohol or a surfactant.

[0091] Furthermore, the alcohol compound is one or a combination of ethanol, ethylene glycol, propylene glycol, isopropanol, and polyvinyl alcohol; the surfactant additive is one or a combination of fatty alcohol polyoxyethylene ether ammonium sulfate, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate; the seed crystal is a Beta molecular sieve seed crystal, a Y-type zeolite seed crystal, or a combination thereof; and the mass of the seed crystal accounts for 2wt%-15wt% of the gel mass.

[0092] Furthermore, the temperature at which the silicon source, aluminum source, alkali source, and water are mixed is 25℃-80℃, the aging time is 2h-6h, the crystallization temperature is 110℃-180℃, and the crystallization time is 10h-96h.

[0093] Furthermore, the crystallization is segmented and / or dynamic crystallization, wherein the first segment of the segmented crystallization has a temperature of 115℃-135℃ and a crystallization time of 10h-24h, and the second segment has a temperature of 140℃-175℃ and a crystallization time of 14h-72h.

[0094] In some embodiments, the silica-to-alumina ratio of the USY molecular sieve is 10 to 100, for example 20 to 80, 30 to 40.

[0095] In some embodiments, the content of the modified Beta molecular sieve is 10wt%-15wt%.

[0096] In some embodiments, the binder is aluminum sol; the catalyst support is kaolin.

[0097] In some embodiments, the catalyst composition is used as a catalyst.

[0098] In some embodiments, the method is used to perform catalytic cracking or hydrocracking of heavy oil.

[0099] This application also provides a method for preparing modified Beta molecular sieves, comprising the following steps:

[0100] The template agent is completely removed from the raw material Beta molecular sieve containing the template agent to obtain the template agent-free raw material Beta molecular sieve;

[0101] The modified Beta molecular sieve is obtained by cycling the template-removed Beta molecular sieve through at least one or at least two of the following steps: ammonium ion exchange or hydrogen ion exchange, followed by high-temperature calcination or hydrothermal treatment.

[0102] This application also provides a method for synthesizing Beta molecular sieves, the method comprising the following steps:

[0103] Step 1: Add aluminum source, alkali source, and template agent to the solvent in sequence, stir to form a solution, and continue aging to obtain intermediate product A. In Step 1, the aluminum source, alkali source, template agent, and solvent (such as deionized water) are in the following molar ratio: Al2O3:0.1~1.2 Na2O:0.04~0.2 Template agent:40~100 Solvent (such as deionized water).

[0104] Step 2: Take another solvent, add silicon source, seed crystal and additive, stir until completely dissolved, add intermediate product A from step 1, and then add aluminum source to obtain alkaline gel B;

[0105] Step 3: Crystallize the alkaline gel B from step 2 to obtain the Beta molecular sieve;

[0106] The amount of template agent used is 2% to 10% of the aluminum source in molar terms. The particle size of the raw material Beta molecular sieve is 100-300 nanometers. The utilization rate of the aluminum source is greater than or equal to 90%. The utilization rate of the silicon source is greater than or equal to 83%. The crystallinity of the raw material Beta molecular sieve is 90%-160%.

[0107] Furthermore, the crystallinity of the raw material is 93%-160%, the solvent is deionized water, and the crystallization is dynamic crystallization or segmented crystallization;

[0108] In the entire reaction, the silicon source, aluminum source, alkali source, template agent, additive, and deionized water are mixed in a molar ratio of 6–80 (SiO2:Al2O3:0.2–2.0, Na2O:0.02–0.1, template agent:0.01–0.06, additive:80–200) to obtain the alkaline gel, wherein the content of seed crystals in the gel is 1 wt% to 18 wt%.

[0109] Furthermore, the silicon source is one or a mixture of several of water glass, sodium silicate, solid silica gel, and precipitated silica, and the aluminum source is one or a mixture of several of boehmite, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum oxide, and aluminum chloride.

[0110] Furthermore, the alkali source is one or a mixture of two of sodium hydroxide and potassium hydroxide.

[0111] Furthermore, the template agent is one or a mixture of more than one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.

[0112] Furthermore, the additive is an alcohol or a surfactant.

[0113] Furthermore, the alcohol compound is one or a combination of ethanol, ethylene glycol, propylene glycol, isopropanol, and polyvinyl alcohol; the surfactant additive is one or a combination of fatty alcohol polyoxyethylene ether ammonium sulfate, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate; and the seed crystal is a raw material Beta molecular sieve seed crystal, Y-type zeolite seed crystal, or a combination thereof, wherein the mass of the seed crystal accounts for 2wt%-18wt% of the gel mass.

[0114] Furthermore, the temperature at which the silicon source, aluminum source, alkali source, and water are mixed is 25℃-80℃, the aging time is 2h-6h, the crystallization temperature is 110℃-180℃, and the crystallization time is 10h-96h.

[0115] Furthermore, the crystallization is segmented and / or dynamic crystallization, wherein the first segment of the segmented crystallization has a temperature of 115℃-135℃ and a crystallization time of 10h-24h, and the second segment has a temperature of 140℃-175℃ and a crystallization time of 14h-72h.

[0116] This application will be further illustrated by the following embodiments.

[0117] Example

[0118] Example 1

[0119] Rod-shaped, small-crystal Beta molecular sieves with a crystallinity of 96%, a SiO2 / Al2O3 ratio of 120, and a particle size of 160 nm were calcined at 550℃ for 4 hours to remove the template agent. The template-removed Beta molecular sieves were then mixed evenly with dilute hydrochloric acid and deionized water, and hydrogen ion exchange was performed at 80℃ for 2 hours while maintaining the pH of the system at 3-4. The mixture was then filtered, washed, and dried at 120℃ for 12 hours to obtain the hydrogen-form Beta molecular sieves. The hydrogen-form Beta molecular sieves were then calcined at 600℃ for 4 hours. The above ion exchange and high-temperature calcination were repeated once each to obtain the modified Beta molecular sieves. Unless otherwise specified, complete removal of the template agent in this application refers to the template agent content in the Beta molecular sieve product being less than 0.1% after high-temperature calcination, measured by the molecular sieve product reaching constant weight after high-temperature calcination.

[0120] The modified Beta molecular sieve is template-free, has a particle size of 100 nm (as shown in Table 1), and a meso-macropore volume of 0.28 cm³. 3 / g, the volume of mesopores accounts for 50% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 60.

[0121] The modified Beta molecular sieve prepared in this application was used as an additive (10 wt%), along with industrial USY (30 wt%, silicon-to-aluminum ratio 30, purchased from Tianjin Nanhua Catalyst Co., Ltd.), kaolin (45 wt%, China Kaolin Co., Ltd.), and alumina sol (15 wt%, Zibo Alumina Sol Technology Co., Ltd.). After molding, the catalyst was aged at 800℃ with 100% steam for 4 hours. Before formal evaluation, the aged catalyst needed to be sieved to 70-400 mesh and dried at 400℃ for 2 hours. The resulting catalyst exhibited excellent pore structure data, such as a mesopore volume of 0.083 cm³. 3 / g, specific relevant parameters are shown in Table 1 below. The mesopore volume of the catalyst composition is greater than or equal to 25% of the mesopore volume of the modified Beta molecular sieve, and the ratio of the volume of meso-macropores in the catalyst composition to the total pore volume is greater than or equal to 110% of the ratio of the volume of meso-macropores in the modified Beta molecular sieve to the total pore volume.

[0122] The pore structure data of the modified Beta molecular sieve and the prepared catalyst in Example 1 are shown in Table 1.

[0123] Table 1

[0124] Modified Beta molecular sieve catalyst <![CDATA[Total pore volume, cm 3 / g]]> 0.56 0.148 <![CDATA[Intermediate - macropore volume, cm 3 / g]]> 0.28 0.083 The proportion of macropore volume to total pore volume 50％ 56.1％

[0125] Comparative Example 1-1

[0126] Without using modified Beta molecular sieves as an additive, industrial USY was used as the main agent (40 wt%), combined with kaolin (45 wt%) and alumina sol (15 wt%). After molding, it was aged at 800℃ and 100% steam for 4 hours. Before formal evaluation, the aged catalyst needed to be sieved to 70-400 mesh and dried at 400℃ for 2 hours. The catalytic cracking effect is shown in Table 2.

[0127] Comparative Examples 1-2

[0128] Modified Beta molecular sieve (40 wt%) obtained in Example 1 was used as an additive, combined with kaolin (45 wt%) and alumina sol (15 wt%). After molding, it was aged at 800°C and 100% steam for 4 hours. Before formal evaluation, the aged catalyst was sieved to 70-400 mesh and dried at 400°C for 2 hours. The catalytic cracking effect of the catalyst was tested and found to be significant, specifically showing an increase in the total yield of ethylene, propylene, and butene, an increase in gasoline yield, an increase in diesel yield, and a decrease in coke yield. Detailed effects are shown in Table 2.

[0129] The catalytic cracking results of Example 1 and Comparative Examples 1-1 and 1-2 are shown in Table 2.

[0130] Table 2

[0131] Example 1 Comparative Example 1-1 Comparative Examples 1-2 dry air 3.18 3.69 5.67 Ethylene + Propylene + Butene 21.5 19.5 19.6 gasoline 40.6 38.7 37.0 diesel fuel 20.8 18.5 17.4 coke 8.1 10.9 11.7

[0132] The catalyst prepared in Example 1 had a 0.51% lower dry gas yield than Comparative Example 1-1, a 2% higher total yield of ethylene, propylene, and butene, a 1.9% higher gasoline yield, a 2.3% higher diesel yield, and a 2.8% lower coke yield.

[0133] In Comparative Examples 1-2, when the amount of modified Beta molecular sieve added as an additive was 40 wt%, the yields of dry gas and coke increased significantly, which was not conducive to the catalytic cracking reaction.

[0134] Example 2

[0135] Rod-shaped, small-crystal Beta molecular sieves with a crystallinity of 120%, a SiO2 / Al2O3 ratio of 120, and a particle size of 180 nm were calcined at 500℃ for 5 hours to remove the template agent. The template-removed Beta molecular sieves, ammonium sulfate, and deionized water were mixed evenly, and ammonium ion exchange was performed at 90℃ for 1 hour while controlling the pH of the system to 4-5. The mixture was then filtered, washed, and dried at 120℃ for 12 hours to obtain ammonium-type Beta molecular sieves. The ammonium-type Beta molecular sieves were then subjected to hydrothermal treatment at 600℃ for 4 hours. The above ammonium ion exchange and high-temperature hydrothermal treatment were repeated once each to obtain the modified Beta molecular sieves.

[0136] The modified Beta molecular sieve is template-free, has a particle size of 260 nm, and a meso-macropore volume of 0.29 cm³. 3 / g, the volume of meso-macropores accounts for 46% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 100%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 40.

[0137] The modified Beta molecular sieve prepared in this application was used as an additive (15 wt%), along with industrial USY (20 wt%, silicon-to-aluminum ratio 30, purchased from Tianjin Nanhua Catalyst Co., Ltd.), ZSM-5 (10 wt%, silicon-to-aluminum ratio 40, purchased from Tianjin Nanhua Catalyst Co., Ltd.), kaolin (45 wt%, China Kaolin Co., Ltd.), and alumina sol (15 wt%, Zibo Alumina Sol Technology Co., Ltd.). After molding, the catalyst was aged at 800℃ with 100% steam for 4 hours. Before formal evaluation, the aged catalyst was sieved to 70-400 mesh and calcined at 400℃ for 2 hours. The pore structure data are shown in Table 3. The catalytic cracking effect of the catalyst was significant, specifically showing an increase in the total yield of ethylene, propylene, and butene, an increase in gasoline yield, an increase in diesel yield, and a decrease in coke yield. Detailed effects are shown in Table 4. Tests show that the mesopore volume of the catalyst composition is greater than or equal to 33% of the mesopore volume of the modified Beta molecular sieve, and the ratio of the volume of meso-macropores in the catalyst composition to the total pore volume is greater than or equal to 120% of the ratio of the volume of meso-macropores in the modified Beta molecular sieve to the total pore volume.

[0138] The pore structure data of the modified Beta molecular sieve and the prepared catalyst in Example 2 are shown in Table 3.

[0139] Table 3

[0140] Modified Beta molecular sieve catalyst <![CDATA[Total pore volume, cm 3 / g]]> 0.63 0.134 <![CDATA[Mesoporous - macroporous volume, cm 3 / g]]> 0.29 0.080 The proportion of macropore volume to total pore volume 46％ 59.7％

[0141] Comparative Example 2

[0142] ZSM-5 molecular sieve was used as the main agent (35 wt%), combined with kaolin (50 wt%) and alumina sol (15 wt%). After molding, it was aged at 800℃ with 100% steam for 4 hours. Before formal evaluation, the aged catalyst needed to be sieved to 70-400 mesh and calcined at 400℃ for 2 hours.

[0143] The catalytic cracking results of Example 2 and Comparative Example 2 are shown in Table 4.

[0144] Table 4

[0145] Example 2 Comparative Example 2 dry air 3.28 3.41 Ethylene + Propylene + Butene 22.2 20.7 gasoline 38.7 37.1 diesel fuel 21.0 19.1 coke 7.6 8.4

[0146] The catalyst prepared in Example 2 had a 0.13% lower dry gas yield, a 1.5% higher total yield of ethylene, propylene, and butene, a 1.6% higher gasoline yield, a 1.9% higher diesel yield, and a 0.8% lower coke yield compared to Comparative Example 2.

[0147] Example 3

[0148] Rod-shaped, small-crystal Beta molecular sieves with 100% crystallinity, a SiO2 / Al2O3 ratio of 80, and a particle size of 260 nm were calcined at 500℃ for 4.5 h to remove the template agent. The template-removed Beta molecular sieve was then mixed with dilute sulfuric acid and deionized water, and subjected to hydrogen ion exchange at 90℃ for 2 h, controlling the pH of the system to 3-6. The mixture was then filtered, washed, and dried at 120℃ for 12 h to obtain the hydrogen-form Beta molecular sieve. The hydrogen-form Beta molecular sieve was then calcined at 600℃ for 4 h. This process of ion exchange and high-temperature calcination was repeated once each to obtain the modified Beta molecular sieve. The modified Beta molecular sieve was template-free, had a particle size of 260 nm, and a meso-macropore volume of 0.21 cm³. 3 / g, the volume of meso-macropores accounts for 42% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 98%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 120.

[0149] The modified Beta molecular sieve prepared in this application was used as an additive (10 wt%), along with industrial USY (20 wt%, silicon-to-aluminum ratio 16, purchased from Tianjin Nanhua Catalyst Co., Ltd.), ZSM-5 (10 wt%, silicon-to-aluminum ratio 120, purchased from Tianjin Nanhua Catalyst Co., Ltd.), kaolin (48 wt%, China Kaolin Co., Ltd.), and alumina sol (12 wt%, Zibo Alumina Sol Technology Co., Ltd.). After molding, the catalyst was aged at 800℃ with 100% steam for 4 hours. Before formal evaluation, the aged catalyst was sieved to 70-400 mesh and dried at 400℃ for 2 hours to obtain the catalyst composition of this application. The pore structure data are shown in Table 5 below. The catalytic cracking effect of the catalyst was significant, specifically showing an increase in the total yield of ethylene, propylene, and butene, an increase in gasoline yield, an increase in diesel yield, and a decrease in coke yield. Detailed effects are shown in Table 6.

[0150] The pore structure data of the modified Beta molecular sieve and the prepared catalyst in Example 3 are shown in Table 5.

[0151] Table 5

[0152] Modified Beta molecular sieve catalyst <![CDATA[Total pore volume, cm 3 / g]]> 0.50 0.133 <![CDATA[Mesoporous - macroporous volume, cm 3 / g]]> 0.21 0.072 The proportion of macropore volume to total pore volume 42％ 54.1％

[0153] Comparative Example 3

[0154] Without using modified Beta molecular sieves as an additive, industrial USY (20 wt%) was used as the main agent, along with ZSM-5 (20 wt%), kaolin (48 wt%), and alumina sol (12 wt%). After molding, the catalyst was aged at 800°C with 100% steam for 4 hours. Before formal evaluation, the aged catalyst was sieved to 70-400 mesh and dried at 400°C for 2 hours.

[0155] The catalytic cracking results of Example 3 and Comparative Example 3 are shown in Table 6.

[0156] Table 6

[0157] Example 3 Comparative Example 3 dry air 2.8 3.9 Ethylene + Propylene + Butene 20.2 19.1 gasoline 36.5 35.1 diesel fuel 21.7 20.1 coke 8.1 9.9

[0158] The catalyst prepared in Example 3 had a 1.1% lower dry gas yield, a 1.1% higher total yield of ethylene, propylene, and butene, a 1.4% higher gasoline yield, a 1.6% higher diesel yield, and a 1.8% lower coke yield compared to Comparative Example 3.

[0159] In summary, the catalyst composition of this application possesses excellent pore structure data, and the composition exhibits significant catalytic cracking performance, specifically manifested in one of the following ways: increased overall yield of ethylene, propylene, and butene; increased gasoline yield; increased diesel yield; or decreased coke yield. Furthermore, this application also provides a method for preparing modified Beta molecular sieves, various applications of modified Beta molecular sieves as catalyst additives, and demonstrates the significant effectiveness of the catalyst composition in catalytic cracking applications.

[0160] The specific preparation examples of the Beta molecular sieve containing the template agent described in this application are as follows:

[0161] Example 4 (Beta molecular sieve containing template agent)

[0162] This embodiment provides a Beta molecular sieve containing a template agent and its synthesis method. The synthesis method includes the following steps:

[0163] At 45℃, 6g of sodium aluminate was added to 35g of deionized water and stirred until the solution became clear. Then, 20g of sodium hydroxide was added and stirred until the solution became clear again. Next, 3.2g of tetraethylammonium hydroxide was added and stirred for 30 minutes, followed by aging for 4 hours to obtain intermediate product A. 125g of water glass and 160g of H2O were weighed and placed in a beaker. Under stirring in a 50℃ water bath, 12g of Beta seed crystals (3.00%) and 6.0g of ethanol were added sequentially. After complete dissolution, intermediate product A was added, followed by the slow addition of 32.8g of [unspecified substance]. A 30% sodium aluminate solution was stirred for 30 min to obtain alkaline gel B. The molar ratio of the components in the gel reaction mixture was 0.5Na2O:Al2O3:35SiO2:120H2O:0.05tetraethylammonium hydroxide:0.04ethanol. The gel was then placed in a reaction vessel for dynamic crystallization at 120℃ for 10 h and 160℃ for 18 h. After washing and filtration, the gel was dried at 120℃ for 12 h to obtain the Beta molecular sieve containing the template agent.

[0164] The aluminum source utilization rate of the Beta molecular sieve synthesized in Example 4 was 90%, and the silicon source utilization rate was 76%. The relative crystallinity of this Beta molecular sieve was 102%. SEM images of the Beta molecular sieve synthesized in Example 4 (e.g.) Figure 1 As shown in the figure, it can be clearly seen that a molecular sieve with a particle size of 100 nm and a rod shape was synthesized.

[0165] Comparative Example 4

[0166] The synthesis method was followed as described in Example 4, but without the addition of ethanol.

[0167] At 45℃, 6g of sodium aluminate was added to 35g of deionized water and stirred until the solution became clear. Then, 20g of sodium hydroxide was added and stirred until the solution became clear again. Next, 3.2g of tetraethylammonium hydroxide was added and stirred for 30 minutes, followed by aging for another 4 hours to obtain intermediate product A. 125g of water glass and 160g of H2O were weighed and placed in a beaker. 12g of Beta seed crystals (3.04%) were added under stirring in a 50℃ water bath. After complete dissolution, intermediate product A was added, followed by the slow addition of 32.8g of sodium hydroxide. A 30% sodium aluminate solution was stirred for 30 min to obtain alkaline gel B. The molar ratio of the components in the gel reaction mixture was 0.5Na2O:Al2O3:35SiO2:120H2O:0.05tetraethylammonium hydroxide. The gel was then placed in a reaction vessel for dynamic crystallization at 120℃ for 10 h and 160℃ for 18 h. After washing and filtration, the gel was dried at 120℃ for 12 h to obtain Beta molecular sieve.

[0168] The aluminum source utilization rate of the Beta molecular sieve synthesized using Comparative Example 4 was 85%, the silicon source utilization rate was 70%, the relative crystallinity of the Beta molecular sieve was 90%, and the particle size was 330 nm. In this example, no ethanol additive was used, which resulted in poor crystallinity and reduced silicon and aluminum utilization.

[0169] Exemplary embodiments of this disclosure have been specifically shown and described above. It should be understood that this disclosure is not limited to the detailed structures, arrangements, or implementations described herein; rather, this disclosure is intended to cover various modifications and equivalent arrangements contained within the spirit and scope of the appended claims.

Claims

1. A catalyst composition comprising: 5-20 wt% modified Beta molecular sieve, wherein the modified Beta molecular sieve is template-free, the particle size of the modified Beta molecular sieve is 100-300 nm, and the meso-macropore volume of the modified Beta molecular sieve is 0.15-0.40 cm³. 3 / g, the volume of meso-macropores accounts for 40%-60% of the total pore volume, the crystallinity of the modified Beta molecular sieve is 80%-160%, and the SiO2 / Al2O3 ratio of the modified Beta molecular sieve is 20-200. 20-40 wt% USY type molecular sieve; 40-50 wt% of catalyst support, wherein the catalyst support comprises kaolin; 10-20wt% binder; and 0-20wt% ZSM-5 molecular sieve, The total mass of the catalyst composition is 100 wt%. The modified Beta molecular sieve is prepared as follows: The template agent is completely removed from the raw material Beta molecular sieve containing the template agent to obtain the template agent-free raw material Beta molecular sieve; The modified Beta molecular sieve is obtained by cycling the template-removed Beta molecular sieve through at least two of the following steps: ammonium ion exchange or hydrogen ion exchange, followed by high-temperature calcination or high-temperature hydrothermal treatment, wherein the high-temperature hydrothermal treatment is performed at a temperature of 400℃-800℃ and the high-temperature calcination treatment is performed at a temperature of 500℃-800℃. The Beta molecular sieve containing the template agent is prepared as follows: Step 1: Add aluminum source, alkali source, and template agent to the solvent in sequence, stir to form a solution, and continue aging to obtain intermediate product A; Step 2: Take another solvent and add silicon source, seed crystal and additive, stir until completely dissolved, add intermediate product A from step 1, and then add aluminum source to obtain alkaline gel B, wherein the additive is a surfactant. Step 3: Crystallize the alkaline gel B from Step 2 to obtain the Beta molecular sieve containing the template agent. The Beta molecular sieve is rod-shaped, and the crystallization is either dynamic crystallization or segmented crystallization. The amount of the template agent used is 2% to 10% of the aluminum source on a molar basis. The particle size of the Beta molecular sieve containing the template agent is 100-300 nanometers. The utilization rate of the aluminum source is greater than or equal to 90%, the utilization rate of the silicon source is greater than or equal to 83%, and the crystallinity of the Beta molecular sieve is greater than or equal to 93%. The catalyst composition is prepared by the following steps: Step 1: Mix all components evenly, shape, and age in water vapor to obtain the aged composition; Step 2: The aged composition is sieved and calcined to obtain the catalyst composition, wherein the meso-macropore volume value of the catalyst composition is greater than or equal to 25% of the meso-macropore volume value of the modified Beta molecular sieve, and the ratio of the meso-macropore volume of the catalyst composition to the total pore volume is greater than or equal to 110% of the ratio of the meso-macropore volume of the modified Beta molecular sieve to the total pore volume.

2. The catalyst composition according to claim 1, characterized in that, Includes 10-15 wt% modified Beta molecular sieves.

3. The catalyst composition according to claim 1, characterized in that, The silica-to-alumina ratio of the USY molecular sieve is 10 to 100.

4. The catalyst composition according to claim 1, characterized in that, The silica-to-alumina ratio of the USY molecular sieve is 20 to 80.

5. The catalyst composition according to claim 1, characterized in that, The USY molecular sieve has a silica-to-alumina ratio of 30 to 40.

6. The catalyst composition according to claim 2, characterized in that, The mesopore volume of the catalyst composition is greater than or equal to 33% of the mesopore volume of the modified Beta molecular sieve, and the ratio of the mesopore volume of the catalyst composition to the total pore volume is greater than or equal to 120% of the ratio of the mesopore volume of the modified Beta molecular sieve to the total pore volume.

7. The catalyst composition according to claim 1, characterized in that, The binder is aluminum sol; the catalyst carrier is kaolin.

8. A method for carrying out a catalytic cracking reaction, characterized in that, The catalyst composition according to any one of claims 1 to 6 is used as the catalyst.

9. The method according to claim 8, characterized in that, The method is used for catalytic cracking of heavy oil.

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